Vulcanization accelerator and manufacture thereof



' or is ffractioned Patented Jan, 13,1931 I vunenivrnncnion ACCELERATOR NoIDrawing. Application filed June'18,

This invention relates to a process of makv ing an 'acetyleneeaniline product useful as an acceleratorjin the vulcanizing, of rubber. According .to the present inventiomacety lene and aniline are reacted together, in

, presence of'an effective catalyst. Theacetylene-aniline' product" t-hus obtained, which contains quinaldine and-other compounds, is combined as a whole with asuitable aldehyde nd suitablefr-a'ctions cont,

bined with an aldehyde. I I t The acetylene-aniline reaction is obtained by passing acetylene. into aniline, preferably anhydrous, in v presence: of cuprous chloride or other suitable catalyst. Thereaction will commence spontaneously/but may be eX- pedited by ,flieating; the temperaturelbeing. preferably maintained between 1-60? and 120 C. but the, reaction will-.proceed- 'at, temperatures. above I and; below this range.

' A temperature-which has "been found satis factory is about: 9090." =Underthese conditions, approximately one molecule of acetylene is combined for eachmolecule of aniline present. The reaction may be conducted at atmospheric pressure or higher pressure.

The reaction may now. be distilled for removal' of uncombined aniline and, if de sired, fractioned for separation of various components of the product. The fractions collecting between 200 and 275 C. have been found especially useful. r

The fractions collecting between 200 and 240 are secondary bases, such as ethyl aniline and butyl aniline, while thefractions collecting between240 and 27 5? are mostly quinaldine or its derivatives. 1 a

After removal of the excess aniline, the

' crude reaction product or selected fractions thereof is caused to react with an aldehyde by bringingthe two together. The reaction is spontaneous atthe outsetbutis afterwards preferably heated, until reaction substantially ceases. An un'combined aldehyde 4 may be distilled 0 a f 3- id flsaizgt HOWARD w. 'MArnnsoiv'; or MonrnnALidonned}:fonnnbafiissieivon ro L T -IBQD Q S me I l EP i M R- A CANADA, it

ANPMANUFACTU'BE E E 1926. were; nears. d

tlnitheicaseiof ethyl aniline theraetie d .With'acetaldehyde' is believed to be:z C rI' NHei-norn-t 0110011 f :i i l C H NH. CH .C H: CI-LCHQ' andinithe case of quinal'dinetobez I t aste tiieirm'cfiea basses P200 and24t0? may be'represented by theformula o6H.N H.oH GH -in which case the met r.

dehyde p'roducti'would be;

I oensni-rononzoi oiig i i The material is considerably more active a than aldehyde ammonia "as an acceleratm but :not quite asjactive as; hexamethylinetetraininef or diphenylguanidine. V

f Th'e' following examples are i'llustrativefof various methodsof practising the invention, 1

butit will be understood. that-the invention 7 is not confined to the details thereof which are explanatory and given without ,limitatiye i w p TEWWZM One hundred parts of aniline' is placed inxa-suitable vessel withfappronimately two parts" of-[anhydrous\cup'rous chloride and heated to approximately, 90 C. Acetylene is passed into the liquid and the reaction is heated as'm'ay be necess'aryito maintain an efficient rate of reaction. The aCetylenesupp1y-iscontinued untilthe reaction substan rainwater uncombined aniline.

ne hundred parts of so tially ceases." The product is"distilled for;'

the acetyleneaniline:

of uncombined aniline) condensed with twenty parts of acetaldehyde under a reflux condenser. The reaction is spontaneous at thev tse n la r h ated; r i ea on a water bath; When reaction fsub stan tially ceases, any uncombinedaldehyde may be distilled off. I

Example I] I The reaction is conducted'as in Example I, except that fifty parts of acetaldehyde are used;

Example If! The acetylene-aniline product obtained as in Example ,I (after .distilling :otf uncombined aniline), before being condensed with aldehyde, is fractionally distilled and fracvtions collecting between 200 and 275 C.

r or heptaldehyde.

presence of a catalyst. I I I 2. A process which comprisescondensing with acetaldehyde the product obtained :by

are "treated with acetaldehyde in the mann'er already explained. Varying proportions of aldehyde maybe used. I \I I The proportions of aldehyde combined r with the acetylene-aniline.productanay be varied considerably from those given in the examples, either less or more, and fractions of the product/other than specified in Example III may be'condensed with varying prowithout first removing uncombined aniline from the crude reaction product.

I-Ia-lvin'g thusdescr bed my invention, what I claim is I 1. A process which comprises condensing with an aldehyde the product obtained by reacting together acetylene and aniline at a temperature between 60 and (lfin reacting together acetylene and; aniline at a temperature between 60 and 120 C ih presence ofacataly'st. I I I I I II 8. A process whichcomprisescondensing with an aldehyde the product obtained 'b'y reacting together acetylene and aniline "ata temperature between 60 and 120 C. in

presence of cuprous chloride .as catalyst.

4. process which comprisescondensing' with acetaldehyde theproduct obtained by reacting together acetylene and aniline at a temperature between and 120 .C. in presence of cuprouschloride as catalyst.- 5. A process which comprises condensing with 'an aldehyde the product obtained reacting together acetylene andfan iline Sat a temperature between 60 and 120 C. in

presence ofa catalyst, after "distilling' oif uncombined aniline. I I I I I 6. A process which comprises condensing with acetaldehyde theproduct obtained by reacting together acetylene and" aniline at a temperature between 60 and 120 in presence of a catalyst, fafter distilling oflf.

uncombined aniline.-

7. A process which comprises condensing with analdehyde those fractions which colwith acetaldehyde those fractions which c0llect between 200 and 275 C. of a product obtained by reacting together acetylene and aniline at a temperature between 60 and 120 C. in presenceof a catalyst, after dis- Htillingofi uncombined'ani-line. I I I, 9. A compos t oniof matterbelng the condensa'tion product of an aldehyde andthe product of acetylene and aniline reacted at a temperature between 60 and 120 C.

10..A composition-0f matter being-the condensation product of an aldehyde and the product resulting from passing acetyleneinto aniline at a temperature between 60 and 120 C. in presence'of'cuprous chloride.

11. A' composition of matter being the condensation product or acetaldehyde and the product resulting-from passing acetylene into aniline at a temperature between 60 and 120 C.- in pre senc'e'of cuprous chloride. 12. A composition of matter being the condensation product; of an aldehyde and the fractions collected between 200 and 275 'C'. from the-distillationof a product resulting from the passage of acetylene into aniline at a temperature between 60 and- 120 Ci inpresence of'a'neffective catalyst. 13. A conipositionflof matter being the condensation product of acetaldehyde and the fractions collected between 200 and 275C. from the distillation-of a product resulting fromthe passage of acetylene into aniline at a temperature between 60 and 120C. presence of an effective catalyst. In. witness whereof, I have hereunto set my hand. 

